Polymethyleneiminoalkanols



POLYNETHYLENEIMINOALKANOLS Frederick F. Blicke, Ann Arbor, Mich.,assignor to Regents of The University of Michigan, Ann Arbor, Mich., acorporation of Michigan No Drawing. Application April 17, 1953, SerialNo. 349,560

6 Claims. (Cl. 260239) This invention relates topolymethyleneiminoalkanols containing from six to eight carbon atoms inthe ring, to lower-alkyl-substituted derivatives thereof, and to acidaddition and quaternary ammonium salts thereof.

This application is a continuation-in-part of my priorfiled applicationSerial 182,125, filed August 29, 1950, now abandoned.

The basic alcohols herein described are generally mobile liquids,readily soluble in most organic solvents, but sparingly soluble inwater. They readily form addition salts with acids, such as, forexample, hydrochloric, hydrobromic, nitric, sulfuric, acetic, lactic,picric, formic, tartaric, et cetera, and quaternary ammonium salts withappropriate compounds, such as, for example, methyl iodide, propylbromide, dimethyl sulfate, ethyl bromide, et cetera. The acid additionsalts are generally crystalline solids, soluble in Water. The compoundsof this invention are useful polymerization inhibitors and chainstoppers.

One method of preparing the compounds of the present invention isillustrated by the following example, which is not to be construed aslimiting.

Example 1 -(beta-hydrxyethyl) -hexameihyleneimine Hexamethyle'neimine[77.5 grams (.782 mole)] was placed in a SOS-milliliter flask equippedwith a reflux condenser and a dropping funnel. The amine was heated on asteam bath and ethylene chlorohydrin [63.0 grams (.7.82 mole)] addeddropwise over a period of one and one-half hours to the materialmaintained at a temperature of about 100 degrees centigrade. Acrystalline mass formed which went back into solution. After heating ona steam bath overnight, the mixture was cooled and crystals obtained.Thirty-five grams of sodium hydroxide and sixty milliliters of waterwere added to the mixture and it was thereafter extracted with a175-rnilliliter portion and three times with 45-milliliter portions ofbenzene. The extracts were combined and after drying over potassiumcarbonate, the benzene was distilled olf at a pressure of about twentymillimeters of mercury absolute. There was thus obtained 71 grams (63.6percent of the theoretical yield) of N-(beta hydroxyethylyhexarnethyleneirnine, boiling at 114 degrees centigrade at 23millimeters of mercury absolute, index of refraction n 1.48l.

The compounds of the present invention may be prepared by the reactionof a suitable halohydrin with a suitable polymethyleneimine. Thereaction may be can ried out with or without the use of an inertdiluent, such as, for example, chloroform, methanol, benzene, or water.The inclusion in the reaction mixture of an acid binding agent, such asan excess of the amine, an alkali metal hydroxide, or other alkali oralkaline salt is preferred. 'The reaction is carried out by mixing thereactants together either in substantially equimolecular proportions orusing an excess of the amine. In certain cases, the reaction is somewhatexothermic and the reagents are preferably mixed slowly with cooling andmeat agitation, so as to maintain the temperature of the mixture at fromabout thirty degrees to about 120 degrees centigrade, depending upon,among other factors, the boiling point of any diluent included withinthe reaction mixture.

Further examples of the preparation of certain compounds within thescope of this invention are as follows, which examples are not to beconstrued as limiting.

2.N-( bera-hydr0xyethyl) -4-methylhexamethyleneimine Example In a mannersimilar to that of Example 1, 34.8 grams of 4-methylhexamethyleneimineand 26.6 grams of etlr ylene chlorohydrin were condensed to give a 61.3percent yield of N-(beta-hydroxyethyl)-4-rnethylhexamethyleneimine,boiling at 102 to 103 degrees Centigrade at ten millimeters of mercuryabsolute. 2.5 grams or" the unreacted imine were recovered, indicating a66.1 percent conversion.

Example3.-N (beta hydroxyethyl) 2 methylhexamethyleneimine In a mannersimilar to that of Example 1, 2-metl tyle hexamethyleneimine [56.6 grams(.5 mole)] and 4.4.3 grams (.55 mole) of ethylene ch'lorohydrin werereacted to give a 51 percent yield of N-(beta-hydroxyethyl)-2-methylhexamethyleneimine, boiling at 123 degrees centigrade at 32millimeters of mercury absolute.

Example 4.-N (gamma hydroxypropyt') 2 methylhexamethyleneimine Example5.-N (beta hydroxyetr'zyl) 2 isopropyi- 5 methylhexamethyleneimine In amanner similar to that of Example 1, ethylene chlorohydrin [8.05 grams(0.1 mole)] was reacted with 15.5 grams (0.1 mole) of2-iso-propyl-5-methylhexamethyleneimine to yield 10.1 grams (52 percentof the theoretical yield) of N-(beta-hydroxyethyl)-2-isopropyl-S-methylhexamethyleneimine, boiling at -87 degrees centigrade at apressure of two millimeters of mercury absolute.

Example 6.N (beta methyl beta izydroxyetl yb octamethyleneimineOctamethyleneimine [10.5 grams (0.083 mole)], 12.0 grams (0.11 mole) ofanhydrous sodium carbonate, milliliters of benzene and 25 milliliters ofmethyl alcohol were placed in a ZOO-milliliter, three-necked flask, towhich a condenser, a stirrer and a dropping funnel were attached,stirred and 10.0 grams (0.086 mole) of pro pylene bromohydrin addedslowly. The mixture was stirred, refluxed for twelve hours, cooled in anice bath, 100 milliliters of water added, and the contents of the flaskpoured into a one liter beaker. The mixture was acidified withconcentrated hydrochloric acid, the organic layer separated, the acidicsolution made alkaline and extracted with three thirty-milliliterportions of ether, The ether extracts were dried .over anhydrous'sodiumsulfate and distilled to yield 7.1 grams .7 percent of the theoreticalyield) of N-(beta-methyl-beta-hydroxyethyl) octamethyleneimine, boilingat 127429 degrees centigrade at fifteen milliliters of mercury absolute;11 1.4800.

The picrate salt formed in ether solution as hereinafter described,melted at 137-138 degrees centigrade after recrystallization from amixture of methyl ethyl ketone and ether.

Analysis: Calculated for C17H2sOaN4: C, 49.27; H, 6.33; N, 13.52.

Found: 49.26; 6.95; 13.80.

Example 7.--N-(gamma-hydroxypropyl)-octamethyleneimineOctarnethyleneimine [6.4 grams (0.05 mole)], 7.8 grams (0.075 mole) ofanhydrous sodium carbonate, 100 milliliters of benzene and 25milliliters of methyl alcohol were treated in a manner similar to thatof Example 6 to yield 5.3 grams (58 percent of the theoretical yield) ofN-(gamma-hydroxypropyl)-octamethyleneimine, boiling at 144-148 degreescentigrade at fifteen millimeters of mercury absolute; n 1.4880.

The picrate salt formed in ether solution melted at 88-89 degreescentigrade after recrystallization from methyl ethyl ketone-ether.

Analysis: Calculated for C1'zH2eOsN4: C, 49.27; H, 6.33; N, 13.52.Found: 49.51; 6.61; 13.47.

Example 8 .-N beta-hydroxyethyl -ctamethyleneimine Octamethyleneimine[18.2 grams (0.14 mole)], 18.2 grams (0.17 mole) of sodium carbonate,200 milliliters of benzene-and fifty milliliters of methyl alcohol weretreated in a manner similar to that of Example 6, to yield 18.7 grams(72 percent of the theoretical yield) of N- (beta hydroxyethyl)octamethyleneimine, boiling at 112-116 degrees centigrade at ninemillimeters of mercury absolute; n 1.4860.

The hydrochloride melted at 83-84 degrees centigrade afterrecrystallization from methyl ethyl ketone.

Analysis: Calculated for C1oH22ONCl: N, 6.75; Cl, 17.11.

Found: 6.78; 17.01.

Example 9.--N-(beta-methyl-beta-hydroxyethyl)- heptamethyleneimineHeptamethyleneimine [45.2 grams (0.4 mole)] and fifty milliliters ofbenzene were placed in a 200-milliliter, three-necked flask, to which acondenser, stirrer and a dropping funnel were attached, stirred, and27.8 grams (0.2 mole) of propylene bromohydrin added. The mixture wasstirred, refluxed for two hours, cooled in an icebath, and ten grams ofsodium hydroxide dissolved in 100 milliliters of water added. Theorganic layer was separated and the aqueous portion extracted with twofifty-milliliter portions of ether. The organic layer and ether extractswere combined, dried over anhydrous magnesium sulfate and distilled,yielding 28.7 grams (84 percent of the theoretical yield) ofN-(beta-methyl-betahydroxyethyl)-heptamethyleneimine, boiling at 109-112degrees centigrade at eleven millimeters of mercury absolute; 11 1.4743.

The hydrochloride melted at 110-111 degrees centigrade afterrecrystallization from ethyl alcohol-ether.

Analysis: Calculated for CH22ONC1: N, 6.75; CI, 17.11. Found: 6.73;17.15.

Example 10.N-(gamma-hydroxypropyl) -heptamethyleneimineHeptamethyleneimine [18.5 grams (0.16 mole)], 100 milliliters of benzeneand 11.4 grams (0.08 mole) of trimethylene bromohydrin were treated in amanner similar to Example 9 to yield 11.1 grams (79 percent of thetheoretical yield) of N-(gamma-hydroxypropyl) -hepta methyleneimine,boiling at 121-124 degrees centigrade at nine millimeters'of mercuryabsolute; 1.4847.

4 The hydrochloride melted at 102-103 degrees centigrade afterrecrystallization from acetone-ether.

Analysis: Calculated for CroHzzONCl: N, 6.75; Cl, 17.11. Found: 6.71;17.04.

Example 11 .-N-( beta-hydroxyethyl) -heptamethyleneimineHeptamethyleneimine [28 grams (0.25 mole)] and 15.6 grams (0.125 mole)of ethylene bromohydrin, were treated in a manner similar to that ofExample 9 to yield 17.1 grams (87 percent of the theoretical yield) ofN- (beta hydroxyethyl) heptamethyleneimine, boiling at 109-112 degreescentigrade at fourteen millimeters of mercury absolute; n 1.4829.

The hydrochloride melted at 76-77 degrees centigrade afterrecrystallization from ethyl alcohol-ether.

Analysis: Calculated for CsHzoONClZ N, 7.23; Cl, 18.34.

Found: 7.24; 18.22.

Example 12.N-(beta-methyl-beta-hydroxyethyl)- hexamethyleneimineHexamethyleneimine [65.0 grams (0.66 mole)] was placed in a200-milliliter, three-necked flask, to which a condenser, a stirrer anda dropping funnel were attached, stirred and 31.5 grams (0.33 mole) ofpropylene chlorohydrin was added slowly. The mixture was stirred, heatedfor four hours on a steam bath, cooled in an icebath and 18 grams ofsodium hydroxide, dissolved in milliliters of water, was added. Theorganic layer was separated and the aqueous portion extracted with twofifty-milliliter portions of ether. The organic layer and etherextracted were combined, dried over anhydrous magnesium sulfate anddistilled, yielding 32.5 grams (63 percent of the theoretical yield) ofN-(beta-methyl-betahydroxyethyl) hexamethyleneimine, boiling at 97-100degrees centigrade at eleven millimeters of mercury absolute; n 1.4680.

The hydrochloride melted at 131-132 degrees centigrade afterrecrystallization from isopropyl alcohol-ether.

Analysis: Calculated for CsHzoONCl: N, 7.23; Cl, 18.34. Found: 7.19;18.31.

Example 13.-N-(gamma-hydroxypropyl)-hexamethyleneimineHexamethyleneimine [39.6 grams (0.4 mole)] and 18.9 grams (0.2 mole) totrimethylene chlorohydrin were treated in a manner similar to that ofExample 12 to yield 28 grams (89 percent of the theoretical yield) of N-gamma hydroxypropyl) hexamethyleneimine, boiling at 112-114 degreescentigrade at nine millimeters of mercury absolute; n 1.4825.

The hydrochloride melted at 153-154 degrees centigrade afterrecrystallization from isopropyl alcohol-ether.

Analysis: Calculated for C9H20ONC1: N, 7.23; Cl, 18.34. Found: 7.31;18.22.

Example ]4.-N-(beta-methyl-beta-hydroxyethyl) -2-methylhexamethyleneimine Z-methyIheXam ethyIeneimine [11.3 grams (0.1mole)] and 13.9 grams (0.1 mole) of propylene bromohydrin were treatedin a manner similar to that of Example 12 to yield ten grams (59 percentof the theoretical yield) of N (beta methyl beta hydroxyethyl) 2methylhexamethyleneimine, boiling at 96-98 degrees centigrade at sevenmillimeters of mercury absolute; 11 1.4670.

The methiodide, obtained from an ethereal solution of the free base andmethyl iodide, melted at 180-181 degrees centigrade afterrecrystallization from methyl ethyl ketone.

Analysis: Calculated for C11H24ONI: N, 4.47; I, 40.52. Found: 4.49;40.44.

Example 15.N- (beta-methyl-beta-hydroxyethyl) -4-methylhexamethyleneimine 4-methylhexamethyleneimine [11.3 grams (0.1mole)] and 13.9 grams (0.1 mole) of propylene bromohydrin were treatedin a manner similar to that of Example 12 to yield 121 grams (71 percentof the theoretical yield) of N (beta methyl beta hydroxyethyl) 4methylhexamethyleneimine, boiling at 101-104 degrees centigrade attwelve millimeters of mercury absolute; n 1.4643.

The hydrochloride melted at 105-106 degrees centigrade afterrecrystallization from isopropyl alcohol-ether.

Analysis: Calculated for CroHzzONCl: N, 6.75; Cl, 17.11. Found: 6.83;17.08.

Example 16.N- (gamma-hydroxypropyl) -4-methylhexamethyleneimz'ne4-methylhexamethyleneimine [11.3 grams (0.1 mole)] and 13.9 grams (0.1mole) of trimethylene bromohydrin were treated in a manner similar tothat of Example 12 to yield 11.3 grams (66 percent of the theoreticalyield) of N- gamma-hydroxypropyl) -4-methylhexamethyleneimine, boilingat 123-127 degrees centigrade at twelve millimeters of mercury absolute;n 1.4780.

The hydrochloride melted at 115-116 degrees centigrade afterrecrystallization from isopropyl alcohol-ether.

Analysis: Calculated for CroHzzONCl: N, 6.75; Cl, 17.11. Found: 6.69;17.22.

Halohydrin, as used in this specification and the appended claims, ismeant to include halo-substituted loweralkanols, wherein the halogen isselected from the group consisting of chlorine, bromine and iodine.Representative halohydrins within the scope of this invention include,for example, ethylene chlorohydrin, trimethylene chlorohydrin, butylenechlorohydrin, amylene chlorohydrin, ethylene iodohydrin, hexylenechlorohydrin, heptylene chlorohydrin, et cetera. Lower-alkyl, as used inthis specification and the appended claims, is intended to include thosealkyl radicals containing up to and including eight carbon atoms, suchas, for example, methyl-, ethyl-, propyl-, isobutyl-, secondary butyl-,tertiary butyl-, amyl-, hexyl-, heptyl-, et cetera.

Acid addition and quaternary ammonium salts of the compoundsabove-described may be prepared by reacting in the presence of asuitable solvent, for example, ether, equimolecular quantities of theiminoalkanol with a suitable acid or quaternarizing compound, andseparating the resulting salt from the reaction mixture in conventionalmanner.

The following example is not to be construed as limiting.

Example 1 7.-N- beta-hydroxyethyl) -hexamethyleneimz'ne acetateApproximately ten grams of N-(beta-hydroxyethyl)- hexamethyleneimine wasdissolved in sixty grams of ether, and 4.4 grams of acetic acid addedthereto. The mixture was dried over anhydrous magnesium sulfate, and theether removed. There was thus obtainedN-(betahydroxyethyl)-hexamethyleneimine acetate, as a crystallinematerial.

Certain of the compounds which serve as intermediates for thepreparation of the compounds are unknown in the art. The followingpreparations illustrate one method which may be employed to preparecertain of the intermediates which can be used to prepare the compoundsof the present invention.

PREPARATION 1.--4-METH YLHEXAMETHYLENEIMINE A mixture of 23.2 grams (.61mole) of lithium aluminum hydride in 400 milliliters of ether was placedin a one-liter, round-bottom, three-necked flask equipped with astirrer, a dropping funnel and a condenser. The mixture was refluxeduntil almost complete solution was obtained and thereafter 77.5 grams(.61 mole) of 4-methylhexamethyleneimine-Z-one dissolved in millilitersof ether added thereto at a rate such that gentle refluxing occurred,which took about two hours. The mixture was thereafter refluxed for twohours with external heating, and cooled in an ice-bath. Fifty-eightmilliliters of water was added slowly to the reaction mixture and it wasthereafter steam distilled. The distillate was salted out with sodiumchloride, separated from the aqueous residue, and the aqueous residueextracted with ether. The ether extracts were added to the organiclayer, the solution dried over potassium carbonate, and the etherremoved therefrom. The mixture was thereafter distilled to give a 75-80percent yield of 4-methylhexamethyleneimine, boiling at -156 degreescentigrade at 745 millimeters of mercury absolute.

PREPARATION 2.-2-METHYLHEXAMETHYLENEIMINE 128.9 grams (1.0 mole) of7-methylhexamethyleneirnine-2-one and 800 milliliters of ether werecontacted with 47.42 grams (1.25 mole) of lithium aluminum hydride in1200 milliliters of ether and refluxed for two hours to yield 67 gramsof Z-methylhexamethyleneimine, boiling at 148-150 degrees centigrade.

PREPARATION 3.2-ISOPROPYL-5-METHYLHEXA- METHYLEN EIMIN E 42.5 grams of7-isopropyl-4-methylhexamethyleneirnine-Z-one was contacted with twentygrams of lithium aluminum hydride in a manner similar to that ofpreparation 1 to give an 83.4 percent yield of 2-isopropyl-5-methylhexamethyleneimine, boiling at 83.5-84.5 degrees centigrade at apressure of fifteen millimeters of mercury absolute.

Various modifications may be made in the compounds and process of thepresent invention without departing from the spirit or scope thereof andit is to be understood that I limit myself only as defined in theappended claims.

I claim:

1. A polymethyleneiminoalkanol selected from the group consisting of (a)those having the formula:

References Cited in the file of this patent UNITED STATES PATENTS WilsonJuly 5, 1949 OTHER REFERENCES Tokura et al.: Chem. Abst., vol. 43, p.2176 (1949). Basileiaclos: Chem. Abst., vol. 32, col. 167 (1938).

1. A POLYMETHYLENEIMINOALKANOL SELECTED FROM THE GROUP CONSISTING OF (A)THOSE HAVING THE FORMULA: